Application of dynamic headspace and gas chromatography coupled to mass spectrometry (DHS-GC-MS) for the determination of oxygenated volatile organic compounds in refinery effluents

• Published in: Analytical methods Vol. 8; no. 17; pp. 3570 - 3577
• Main Authors: Boczkaj, Grzegorz, Makos, Patrycja, Przyjazny, Andrzej
• Format: Journal Article
• Language: English
• Published: 01.01.2016
• Subjects: Alcohols; Dynamics; Effluents; Mass spectrometry; Organic compounds; Oxidation; Oxygenated; Volatile compounds
• ISSN: 1759-9660; 1759-9679
• DOI: 10.1039/c5ay03043a

The paper presents a new procedure for the determination of oxygenated volatile organic compounds (O-VOCs) in postoxidative effluents from the production of petroleum asphalt using dynamic headspace coupled to gas chromatography-mass spectrometry in the selected ion monitoring (SIM) mode (DHS-GC-MS). Among the GC capillary columns tested, a polar SLB-IL111 column with the ionic liquid stationary phase was found to be superior due to its high selectivity for n-alkanes and individual oxygenated volatile organic compounds. The low detection limit, good reproducibility and a wide linear range allows determination of O-VOCs at low concentration levels and applicability of the procedure to routine analyses of O-VOCs in industrial effluents with a very complex composition. The developed procedure was used for the analysis of real samples - raw effluents from the production of bitumens and effluents treated chemically through oxidation. Thirteen compounds at concentrations ranging from 0.01 mu g mL super(-1) to 118.61 mu g mL super(-1) were identified in the effluents. In addition, nine more compounds, mostly alcohols, aldehydes and ketones, were identified using the SCAN mode. The paper demonstrates the need for monitoring O-VOCs in processes of chemical treatment of effluents. Due to the pathways of oxidation of organic pollutants present in effluents, O-VOCs become secondary pollutants. A substantial increase in the concentration of some groups of compounds, i.e.phenol and its derivatives and aliphatic and cyclic alcohols, was found in oxidized effluents. The presence of these compounds has a negative effect on the activated sludge used in refinery wastewater treatment plants.